US4913801A - Passivation of FCC catalysts - Google Patents
Passivation of FCC catalysts Download PDFInfo
- Publication number
- US4913801A US4913801A US07/208,202 US20820288A US4913801A US 4913801 A US4913801 A US 4913801A US 20820288 A US20820288 A US 20820288A US 4913801 A US4913801 A US 4913801A
- Authority
- US
- United States
- Prior art keywords
- cerium
- catalyst
- feedstock
- cracking
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/521—Metal contaminant passivation
Definitions
- This invention relates to the art of catalytic cracking of hydrocarbons, and in particular to methods of inhibiting on zeolite catalysts the detrimental effects of contamination by metals, particularly nickel, which are contained in the hydrocarbon feedstock.
- FCC Fluid Catalytic Cracker
- Major metal contaminants that are found in Fluid Catalytic Cracker (FCC) feedstocks include nickel, vanadium, iron, copper and occasionally other heavy metals.
- the problems associated with metal contamination, particularly nickel, during the catalytic cracking of hydrocarbons to yield light distillates such as gasoline are documented in Oil & Gas Journal of July 6, 1981 on pages 103-111 and of Oct. 31, 1983 on pages 128-134.
- the problems associated with vanadium metal contamination are described in U.S. Pat. No. 4,432,890 and German Pat. No. 3,634,304.
- the invention herein represents an innovation and improvement over those processes set forth and claimed in U.S. Pat. No. 4,432,890 and German Pat. No. 3,634,304.
- Vanadium primarily decreases activity and desirable gasoline selectivity by attacking and destroying the zeolite catalytic sites. Its effect on the activity is about four times greater than that of nickel. Vanadium also increases hydrogen and coke, but at only about one fourth the rate of nickel.
- the reducing atmosphere of hydrogen and carbon monoxide in the cracking zone reduces the nickel and vanadium to lower valence states.
- the nickel is an active dehydrogenating agent under these circumstances, increasing hydrogen and coke which also leads to a small decrease in conversion activity.
- conversion can be increased by changing the catalyst to oil ratio or by increasing the cracking temperature, but coke and hydrogen will also be increased in either case.
- the activity should be kept at a constant level.
- the passivating agents have been added to the catalyst during manufacture, to the catalyst after manufacture by impregnation, to the feedstock before or during processing, to the regenerator, and/or any combination of the above methods.
- cerium passivates vanadium, it was quite unexpectedly found that cerium also passivates the adverse effects of nickel.
- U.S. Pat. Nos. 4,432,890 and 4,513,093 teach that numerous metallic compounds (titanium, zirconium, manganese, magnesium, calcium, strontium, barium, scandium, yttrium, lanthanides, rare earths, actinides, hafnium, tantalum, nickel, indium, bismuth, and tellurium act as vanadium passivators.
- German Pat. No. 3,634,304 claims that yttrium, lanthanides, cerium, and other rare earth compounds passivate the adverse effects of vanadium.
- only titanium was used on an FCC catalyst to show the effects of the various claimed metals on passivating vanadium. Cerium was not specifically mentioned.
- the invention is directed to a process of passivating nickel containing on a zeolitic cracking catalyst.
- the total process generally entails:
- the catalyst during the cracking process in contaminated with from about 100 to 5000 parts nickel per million parts of catalyst, with nickel contained in a feedstock at concentrations of up to about 100 ppm, which nickel would increase hydrogen and coke yields at the cracking temperatures and conditions in the cracking zone, and wherein the catalyst contains less than about 3000 ppm of vanadium; the improvement comprising treating the feedstock containing the nickel contaminant with cerium, with the amount of cerium utilized being from 0.005 to 240 ppm on the nickel in the feedstock and at atomic ratios with nickel of from 1:1 to 0.05:1 Ce/Ni, preferable 0.66:1to 0.1:1.
- cerium compounds which can be used include cerium in the cerous or ceric state with anions of nitrate (designated NO 3 in the examples), ammonium nitrate, acetate, proprionate, butyrate, neopentoate, octoate (Oct), laurate, neodecanoate, stearate, naphthenate, oxalate, maleate, benzoate, acrylate, salicylate, versalate, terephthalate, carbonate, hydroxide, sulfate, fluoride, organosulfonate, acetylacetonate, Beta-diketones, oxide (designated either as O 2 for a water based suspension or as Org for a hydrocarbon based suspension in the examples), ortho-phosphate, or combinations of the above.
- the cerium compound is fed to the feedstock on a continuous basis so that enough cerium is present in the feedstock to passivate the nickel contained therein.
- the cerium concentration in the feedstock will be 0.005 to 240 ppm based on 0.1 to 100 ppm nickel in the feedstock.
- the most desirable manner of treating the cracking catalyst with the cerium will be adding a solution or suspension containing the cerium to the feedstock.
- the solvent used to solubilize or suspend the cerium compound can be water or an organic solvent, preferably a hydrocarbon solvent similar to the hydrocarbon feedstock.
- the concentration of the cerium in the solvent can be any concentration that makes it convenient to add the cerium to the feedstock.
- zeolite crystalline aluminosilicate cracking catalysts were used.
- the catalytic cracking runs were conducted employing a fixed catalyst bed, a temperature of 482° C., a contact time of 75 seconds, and a catalyst to oil ratio of about 3:1 or greater as detailed under the catalyst to oil ratio (C/O) in the individual Tables.
- the feedstock used for these cracking runs was a gas oil feedstock having a boiling range of approximately 500° to 1000° F.
- the four zeolitic cracking catalysts that were used are all commercial catalysts that are described as:
- Each of the four catalysts were conditioned similarly.
- the fresh Catalysts A, C, and D were heated in air to 649° C. for 0.5 hour before metals were added.
- To these conditioned catalysts were added the appropriate ppms of vanadium, and/or nickel, and/or cerium (as designated in the Tables) followed by heating the metals contaminated catalysts in air for 1 hour at 649° C. and then for 6.5 hours in steam at 732° C., or 760° C., or 788° C.
- Catalyst B was heated in air at 649° C. for 0.5 hour before metals were added.
- To the conditioned catalyst was added the appropriate ppms of vanadium and/or nickel and/or cerium (as designated in Table 2) followed by heating the metals contaminated catalyst in air for 1 hour at 649° C. and then for 19.5 hours at 732° C. in steam.
- Predicted hydrogen weight percent data were determined by a least squares linear fit of the vanadium and/or nickel contaminated catalyst runs for each catalyst. Predicted catalyst hydrogen weight percent data were determined by a least squares fit of the fresh catalysts only. The equations determined in each case are given in the appropriate tables.
- Catalyst D the percent changes in hydrogen and coke were reduced when passivated with cerium compounds.
Abstract
Description
Weight % Change Conversion=Wt. % conv. Ce run--Avg. Wt. % conv. metals contaminant runs
TABLE 1 __________________________________________________________________________ Data for FCC Commercial Catalyst A Avg. Actual Molar Ratios % Change In Ce Ce V Ni Nos. Wt. % Wt. % Wt. % Ce/ Ce/ Wt. % Cmpd ppm ppm ppm C/O Test Conv. H.sub.2 Coke Ni V + Ni Conv. H.sub.2 Coke __________________________________________________________________________ Steaming Temperature = 732° C. None 0 0 0 3.00 1 68.9 0.06 1.5 -- -- -- -- -- None 0 3000 1500 3.00 2 55.5 0.59 3.0 0.00 0.00 0 0 0 O.sub.2 3000 3000 1500 3.00 2 54.5 0.60 2.2 0.84 0.25 -1 2 -25 Oct 3000 3000 1500 3.00 2 58.3 0.56 2.6 0.84 0.25 4 -6 -12 None 0 0 3000 3.00 2 65.9 0.63 3.7 0.00 0.00 0 0 0 O.sub.2 1500 0 3000 3.00 2 59.1 0.54 2.2 0.21 0.21 -7 -16 -41 Oct 1500 0 3000 3.00 2 59.7 0.50 2.9 0.21 0.21 -6 -22 -21 Steaming Temperature = 760° C. None 0 0 0 3.03 2 56.5 0.06 1.1 -- -- -- -- -- None 0 0 0 4.44 2 70.5 0.07 3.3 -- -- -- -- -- None 0 0 2000 3.02 4 53.5 0.42 2.4 0.00 0.00 0 0 0 None 0 0 2000 4.44 4 66.2 0.63 2.8 0.00 0.00 0 0 0 None 0 0 2000 5.95 2 75.6 0.94 3.7 0.00 0.00 0 0 0 Oct 1000 0 2000 2.96 1 62.5 0.36 4.2 0.21 0.21 6 -45 71 Oct 1000 0 2000 4.55 2 79.5 0.63 6.8 0.21 0.21 13 -38 146 Oct 2000 0 2000 3.02 1 63.6 0.35 4.5 0.42 0.42 10 -49 86 Oct 2000 0 2000 4.39 1 68.8 0.51 5.1 0.42 0.42 3 -34 85 Oct 3000 0 2000 4.30 1 70.3 0.43 5.8 0.63 0.63 4 -49 110 Oct 3000 0 2000 2.97 1 57.2 0.32 3.7 0.63 0.63 4 -38 52 Steaming Temperature = 788° C. None 0 0 0 2.94 2 49.0 0.04 0.04 -- -- -- -- -- None 0 0 0 4.47 2 71.4 0.06 4.1 -- -- -- -- -- None 0 0 2000 2.96 4 42.4 0.33 2.7 0.00 0.00 0 0 0 None 0 0 2000 4.43 4 56.2 0.56 3.1 0.00 0.00 0 0 0 None 0 0 2000 6.01 2 68.5 0.83 2.6 0.00 0.00 0 0 0 Oct 1000 0 2000 4.56 1 55.3 0.47 3.8 0.21 0.21 -1 -19 21 Oct 1000 0 2000 2.93 1 43.8 0.30 2.2 0.21 0.21 1 -14 -20 Oct 2000 0 2000 3.08 1 45.4 0.27 2.3 0.42 0.42 3 -30 -16 Oct 2000 0 2000 4.54 1 50.0 0.42 3.0 0.42 0.42 -6 -13 -4 Oct 3000 0 2000 3.01 1 43.1 0.27 2.2 0.63 0.63 1 -22 -18 Oct 3000 0 2000 4.57 1 58.4 0.41 3.8 0.63 0.63 2 -33 21 __________________________________________________________________________ Predicted Hydrogen Weight %: at 760° C. = 0.00104*C/O + 0.0226*conv. - 0.823 at 788° C. = 0.0196*C/O + 0.0168*conv. - 0.449 Predicted Cat. H.sub.2 = 0.000778*conv. + 0.0107
TABLE 2 __________________________________________________________________________ Data for FCC Commercial Catalyst B Avg. Actual Molar Ratios % Change In Ce Ce V Ni Nos. Wt. % Wt. % Wt. % Ce/ Ce/ Ce/ Wt. % Cmpd ppm ppm ppm Test Conv. H.sub.2 Coke V Ni V + Ni Conv. H.sub.2 Coke __________________________________________________________________________ Steaming Temperature = 732° C. None 0 0 0 9 74.1 0.08 4.4 0.00 -- -- -- -- None 0 3000 1500 23 62.1 0.46 3.7 0.00 0.00 0.00 0 0 0 NO.sub.3 1500 3000 1500 3 62.8 0.55 2.5 0.18 0.42 0.31 1 32 -31 NO.sub.3 2000 3000 1500 2 61.4 0.49 2.6 0.24 0.56 0.17 -1 16 -19 NO.sub.3 3000 3000 1500 3 64.1 0.38 2.3 0.36 0.84 0.25 2 -16 -38 NO.sub.3 4000 3000 1500 3 66.4 0.52 3.0 0.49 1.12 0.34 4 13 -19 NO.sub. 3 8000 3000 1500 3 64.3 0.54 4.1 0.97 2.25 0.68 2 16 11 O.sub.2 500 3000 1500 5 62.1 0.47 4.0 0.06 0.14 0.04 0 2 10 O.sub.2 1000 3000 1500 4 62.7 0.48 3.7 0.12 0.28 0.08 1 5 2 O.sub.2 1500 3000 1500 2 60.6 0.56 3.3 0.18 0.42 0.13 -2 27 -9 O.sub.2 2000 3000 1500 8 66.1 0.58 3.8 0.24 0.56 0.17 4 26 3 O.sub.2 4000 3000 1500 3 71.6 0.36 3.1 0.49 1.12 0.34 9 -39 -17 O.sub.2 8000 3000 1500 3 67.3 0.45 3.7 0.97 2.25 0.68 5 -11 2 Oct 750 3000 1500 3 65.4 0.48 4.9 0.09 0.21 0.06 3 -8 34 Oct 1500 3000 1500 3 63.3 0.46 4.7 0.18 0.42 0.13 1 -8 29 Oct 3000 3000 1500 2 72.9 0.36 3.8 0.36 0.84 0.25 11 -45 4 Org 1000 3000 1500 3 64.6 0.46 5.3 0.12 0.28 0.08 3 -13 44 Org 2000 3000 1500 3 64.0 0.44 3.5 0.24 0.56 0.17 2 -5 -5 Org 4000 3000 1500 3 62.9 0.48 3.5 0.49 1.12 0.34 1 5 -3 Org 5000 3000 1500 2 68.9 0.47 3.4 0.61 1.40 0.42 7 -8 -7 __________________________________________________________________________ Predicted Weight % H.sub.2 = 0.0070*Conv. - 0.024*Coke - 0.063
TABLE 3 __________________________________________________________________________ Data for FCC Commercial Catalyst C Avg. Actual Molar % Change In Ce Ni Nos. Wt. % Wt. % Wt. % Ratio Wt. % Ce ppm ppm C/O Test Conv. H.sub.2 Coke Ce/Ni Conv. H.sub.2 Coke __________________________________________________________________________ Steaming Temperature = 760° C. None 0 0 3.03 2 67.1 0.08 3.0 -- -- -- -- None 0 0 4.55 2 76.3 0.12 4.5 -- -- -- -- None 0 2000 3.02 4 59.5 0.50 2.4 0.00 0 0 0 None 0 2000 4.49 4 70.7 0.70 3.7 0.00 0 0 0 Oct 1500 2000 2.96 1 55.8 0.41 2.9 0.32 -4 -20 21 Oct 1500 2000 4.45 1 73.9 0.63 3.7 0.32 4 -9 0 Oct 3000 2000 2.94 1 59.9 0.52 2.2 0.63 0 7 -11 Oct 3000 2000 4.43 1 72.5 0.64 3.7 0.63 2 -8 0 Oct 1500 0 2.93 1 59.8 0.07 2.2 0.00 -7 9 -26 Oct 1500 0 4.55 1 72.5 0.12 3.8 0.00 -4 30 -16 Steaming Temperature = 788° C. None 0 0 3.01 2 50.9 0.09 1.9 -- -- -- -- None 0 0 4.55 2 64.5 0.12 2.3 -- -- -- -- None 0 2000 3.06 4 52.8 0.47 2.6 0.00 0 0 None 0 2000 4.50 4 63.3 0.72 3.2 0.00 0 0 Oct 1500 2000 3.00 2 41.7 0.51 2.3 0.32 -11 9 -15 Oct 1500 2000 4.36 1 57.4 0.74 3.7 0.32 -6 6 15 Oct 3000 2000 2.97 1 32.1 0.54 2.3 0.63 -21 15 -15 Oct 3000 2000 4.30 1 56.7 0.61 2.9 0.63 -6 -14 -9 Oct 1500 0 3.08 1 41.3 0.25 1.5 0.00 -10 260 -18 Oct 1500 0 4.49 1 57.5 0.30 2.2 0.00 -7 200 0 __________________________________________________________________________ Predicted Hydrogen Weight %: at 760° C. = 0.162*C/O - 0.00333*conv. + 0.2085 at 788° C. = 0.176*C/O - 0.000597*conv. - 0.0317 Predicted Cat. H.sub.2 : at 760° C. = 0.00404*conv. - 0.19 at 788° C. = 0.00196*conv. - 0.00885
TABLE 4 __________________________________________________________________________ Data for FCC Commercial Catalyst D Avg. Actual Molar Ratios % Change In Ce V Ni Nos. Wt. % Wt. % Wt. % Ce/ Ce/ Wt. % Ce ppm ppm ppm Test Conv. H.sub.2 Coke Ni V + Ni Conv. H.sub.2 Coke __________________________________________________________________________ Steaming Temperature = 732° C. None 0 0 0 4 77.5 0.05 3.6 -- -- -- -- -- None 0 3000 1500 5 64.4 0.56 3.3 0.00 0.00 0 0 0 NO.sub.3 3000 3000 1500 1 68.4 0.53 3.1 0.84 0.25 4 -6 -7 Oct 3000 3000 1500 1 69.7 0.53 3.4 0.84 0.25 5 -6 2 None 0 0 4000 3 75.6 0.62 4.9 0.00 0.00 0 0 0 NO.sub.3 3000 0 4000 1 72.0 0.52 3.0 0.32 0.32 -4 -18 -39 Oct 3000 0 4000 1 74.8 0.70 3.7 0.32 0.32 -1 14 -24 __________________________________________________________________________
Claims (8)
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/208,202 US4913801A (en) | 1988-06-17 | 1988-06-17 | Passivation of FCC catalysts |
CA000597043A CA1323852C (en) | 1988-06-17 | 1989-04-18 | Passivation of fcc catalysts |
AU35082/89A AU605425B2 (en) | 1988-06-17 | 1989-05-22 | Passivation of fcc catalysts |
DE89306138T DE68908791T2 (en) | 1988-06-17 | 1989-06-16 | Hydrocarbon cracking process. |
EP89306138A EP0347248B1 (en) | 1988-06-17 | 1989-06-16 | Cracking of hydrocarbons |
AT89306138T ATE93884T1 (en) | 1988-06-17 | 1989-06-16 | HYDROCARBON CRACKING PROCESS. |
US07/500,426 US5064524A (en) | 1988-06-17 | 1990-03-28 | Passivation of FCC catalysts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/208,202 US4913801A (en) | 1988-06-17 | 1988-06-17 | Passivation of FCC catalysts |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/500,426 Continuation US5064524A (en) | 1988-06-17 | 1990-03-28 | Passivation of FCC catalysts |
Publications (1)
Publication Number | Publication Date |
---|---|
US4913801A true US4913801A (en) | 1990-04-03 |
Family
ID=22773642
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US07/208,202 Expired - Fee Related US4913801A (en) | 1988-06-17 | 1988-06-17 | Passivation of FCC catalysts |
Country Status (6)
Country | Link |
---|---|
US (1) | US4913801A (en) |
EP (1) | EP0347248B1 (en) |
AT (1) | ATE93884T1 (en) |
AU (1) | AU605425B2 (en) |
CA (1) | CA1323852C (en) |
DE (1) | DE68908791T2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5064524A (en) * | 1988-06-17 | 1991-11-12 | Betz Laboratories, Inc. | Passivation of FCC catalysts |
US5378349A (en) * | 1993-05-26 | 1995-01-03 | Phillips Petroleum Company | Passivated catalysts for cracking process |
US5407560A (en) * | 1992-03-16 | 1995-04-18 | Japan Energy Corporation | Process for manufacturing petroleum cokes and cracked oil from heavy petroleum oil |
US5853568A (en) * | 1997-07-30 | 1998-12-29 | Exxon Research And Engineering Company | Fluid cat cracking heavy using stripped catalyst for feed preheat and regenerator temperature control |
US5935890A (en) * | 1996-08-01 | 1999-08-10 | Glcc Technologies, Inc. | Stable dispersions of metal passivation agents and methods for making them |
US20110132808A1 (en) * | 2011-01-12 | 2011-06-09 | Basf Corporation | Rare Earth-Containing Attrition Resistant Vanadium Trap for Catalytic Cracking Catalyst |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0514597A1 (en) * | 1989-11-08 | 1992-11-25 | Texaco Development Corporation | Reduction of sulfur content in regenerator off gas of a fluid cracking unit |
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-
1988
- 1988-06-17 US US07/208,202 patent/US4913801A/en not_active Expired - Fee Related
-
1989
- 1989-04-18 CA CA000597043A patent/CA1323852C/en not_active Expired - Fee Related
- 1989-05-22 AU AU35082/89A patent/AU605425B2/en not_active Ceased
- 1989-06-16 AT AT89306138T patent/ATE93884T1/en active
- 1989-06-16 DE DE89306138T patent/DE68908791T2/en not_active Expired - Fee Related
- 1989-06-16 EP EP89306138A patent/EP0347248B1/en not_active Expired - Lifetime
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Cited By (9)
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US5064524A (en) * | 1988-06-17 | 1991-11-12 | Betz Laboratories, Inc. | Passivation of FCC catalysts |
US5407560A (en) * | 1992-03-16 | 1995-04-18 | Japan Energy Corporation | Process for manufacturing petroleum cokes and cracked oil from heavy petroleum oil |
US5378349A (en) * | 1993-05-26 | 1995-01-03 | Phillips Petroleum Company | Passivated catalysts for cracking process |
US5935890A (en) * | 1996-08-01 | 1999-08-10 | Glcc Technologies, Inc. | Stable dispersions of metal passivation agents and methods for making them |
US5853568A (en) * | 1997-07-30 | 1998-12-29 | Exxon Research And Engineering Company | Fluid cat cracking heavy using stripped catalyst for feed preheat and regenerator temperature control |
US20110132808A1 (en) * | 2011-01-12 | 2011-06-09 | Basf Corporation | Rare Earth-Containing Attrition Resistant Vanadium Trap for Catalytic Cracking Catalyst |
US9029291B2 (en) | 2011-01-12 | 2015-05-12 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
US9637688B2 (en) | 2011-01-12 | 2017-05-02 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
US10066170B2 (en) | 2011-01-12 | 2018-09-04 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
Also Published As
Publication number | Publication date |
---|---|
DE68908791T2 (en) | 1993-12-16 |
EP0347248B1 (en) | 1993-09-01 |
DE68908791D1 (en) | 1993-10-07 |
ATE93884T1 (en) | 1993-09-15 |
AU605425B2 (en) | 1991-01-10 |
AU3508289A (en) | 1989-12-21 |
EP0347248A1 (en) | 1989-12-20 |
CA1323852C (en) | 1993-11-02 |
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